JPH02264946A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce color stains and color fog of a sensitive material by incorporating a specified compound. CONSTITUTION:This sensitive material contains at least one of the substantially colorless compounds and their alkali precursors, and the compounds are represented by formula I in which each of R<1> and R<2> is H, alkyl, or the like; R<3> is alkylene; each of R<4> - R<7> is H, alkyl, or the like; X is -NHCO-, -NHSO2-, or the like; and each of m and n is 0 or 1. The compound can be added to an interlayer between emulsion layers different in color sensitivity, and it can be embodied by a compound of formula II and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide color photographic material, and more particularly to a silver halide color photographic material with improved color staining and color fog.

(Prior art) After exposing a silver halide color photographic light-sensitive material, aromatic first
A method of forming a color image by processing with a color developer containing a grade amine developing agent is well known.

In such a color image forming method, the above-mentioned developing agent is oxidized by oxygen in the air, and this oxidized developing agent reacts with the color coupler in the unexposed or low-exposed areas of the photosensitive material to form a dye. It is well known that color fogging occurs.

In addition, in ordinary color sensitive materials that have two or more emulsion layers containing color couplers with different color sensitivities and different hues, the oxidized developing agent generated during development in one color-sensitive layer is transferred to the other layer. It is also known that it diffuses into the color-sensitive layer and reacts with couplers, causing color contamination (color mixing).

As one means for preventing these undesirable color fogs and color stains, a method using a hydroquinone compound has been proposed.

For example, U.S. Patent No. 2,360.290, U.S. Pat.
No. 9,631, No. 2,403.721, No. 3,960
．． No. 570, etc., mono n-alkylhydroquinones are frequently used, U.S. Pat.
No. 6329, No. 50156438, West German Patent Publication 2,
Monobranched alkylhydroquinones are disclosed in U.S. Pat. No. 149,789, U.S. Pat.
2.300, same 3. ．． No. 243,294, 3700
．． No. 453, British Patent No. 752,146, Japanese Unexamined Patent Publication No. 1973-
No. 156438, No. 53-9528, No. 54-296
No. 37 and Japanese Patent Publication No. 50-21249, dialkyl-substituted hydroquinones are disclosed in U.S. Pat. ．． 418,613
The issue describes arylhydroquinones.

Although these compounds do have some effect in preventing color fogging and color staining, the effect is small and there is a problem in that colored substances are produced after the preventive effect is achieved.

Therefore, acyl group, nitro group, cyano group, formyl group,
Hydroquinones nuclearally substituted with electron-withdrawing groups such as halogenated alkyl groups have been proposed in US Pat. No. 4,198,239. Although these are certainly excellent in their ability to prevent color staining, they have problems such as producing colored substances, deteriorating performance during the production and storage of sensitive materials, and fogging of silver halide emulsions.

In addition, hydroquinones substituted with aliphatic acylamino groups, ureido groups, urethane groups, etc. are disclosed in U.S. Pat.
No. 8,239.

It is true that these compounds have a certain degree of ability to prevent color staining.
There was also less coloring. However, its ability to prevent color staining is still insufficient, and there are also problems with storage stability, such as precipitation of crystals during the production of sensitive materials.

Furthermore, hydroquinones substituted with an alkyl group, an aralkyl group, or an acylamino group having a sulfonic acid group are proposed in U.S. Patent No. 2,701,197, but these compounds are added during the production and storage of sensitive materials. This has the disadvantage that it not only deteriorates the color stain prevention ability and color fog prevention ability of the additive layer, but also changes the photographic performance of other layers during manufacturing and storage.

Furthermore, JP-A-59-202465 describes hydroquinones substituted with sulfonamide groups,
Its ability to prevent color staining was still insufficient.

Further, JP-A No. 57-22237 proposes hydroquinones having an electron-withdrawing group, such as hydroquinone substituted with a carbamoyl group, but these compounds are easily oxidized during the production and storage of sensitive materials. There were problems such as changes in photographic performance and a high degree of coloration of the oxidant.

Furthermore, methods for using hydroquinone similar to the compound of the present invention are described in U.S. Pat. No. 3,930,866
The compound of the present invention is not specifically described in this issue. Further, US Pat. No. 4,277.558 discloses the use of hydroquinone and quinone in combination, and when the compound of the present invention is used in such a method, the ability to prevent color staining is actually reduced. Further, the compounds of the present invention are not specifically exemplified.

Japanese Patent Publication No. 55-7578 relates to a compound having a hydroquinone residue and a coupler residue in the same molecule, which forms a color image due to a coupling reaction during the development process, which is not the object of the present invention. The properties of preventing color contamination and color capri are incompatible with each other.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a photosensitive material with less color staining and color fog, and the second object is to provide a photosensitive material with less color staining and color fogging. The third objective is to provide a photosensitive material containing an agent that prevents color staining, and the third objective is to exhibit stable photographic performance over a long period of time without changing its ability to prevent color staining and color capri during manufacturing and/or storage. The fourth objective is to provide a photosensitive material with excellent color reproducibility, and a fourth object is to provide a photosensitive material with a thin emulsion layer and a thin intermediate layer.

(Means for Solving the Problems) The above aspects of the present invention include a silver halide color photographic light-sensitive material containing a substantially colorless compound represented by the following pattern (I) or an alkali precursor thereof. This was achieved by

υH In the formula, R1 and RZ are hydrogen atoms, halogen atoms, each substituted or unsubstituted alkyl group, aryl group, acylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, carbamoyl group , or represents a sulfamoyl group, and R1
and R2 may jointly form a carbocycle or a heterocycle.

R3 represents a substituted or unsubstituted alkylene group. R4R
3, R6, R? is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, an acylamino group, a sulfonamido group, an alkoxy group, a monoloxy group, an alkylthio group, an arylthio group, an amino group, Does not represent an acyl group, acyloxy group, carbamoyl group, carbamoylamino group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic group, alkoxysulfonyl group or aryloxysulfonyl group.

However, R5 is not a hydroxyl group, and two adjacent groups may jointly form a carbocycle or a heterocycle.
x is -NHCO--NHCONH-1-CONH-1N
H5O! --NH5O*NH- Represents Hll-5O1N-1 or -0-C-, and m and n each independently represent 0 or 1.

R1, R? The total number of carbon atoms is 8 or more.

The present invention will be explained in further detail.

In the formula (I), R+ and Rz are a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom), a substituted or unsubstituted alkyl group (carbon number 1-60, e.g. methyl, t- Butyl, t-octyl, cyclohexyl,
n-hexadecyl, 3decanamidopropyl, 1.1-
Dimethylbenzyl, phenethyl), aryl group (6 to 60 carbon atoms, e.g. phenyl, P-)lyl), acylamino group (2 to 60 carbon atoms, e.g. acetylamino, n-butanamide, 2-hexadecaneamide, 2(2', 4'-
di-L-amylphenoxy)butanamide, benzoylamino), alkoxy groups (carbon atoms 1 to 600, e.g. methoxy, ethoxy, butoxy, n-octyloxy, methoxyethoxy), aryloxy groups (carbon atoms 6 to 60, e.g. phenoxy, 4-t -octylphenoxy), alkylthio groups (1 to 60 carbon atoms, e.g. butylthio, hexadecylthio), arylthio groups (6 to 60 carbon atoms, e.g. phenylthio, 4-dodecyloxyphenylthio),
Acyl group (2 to 60 carbon atoms, e.g. acetyl group, benzoyl group, lauroyl group, etc.), sulfonyl group (1 carbon number
~60° e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, dodecylbenzenesulfonyl)
, carbamoyl group (carbon number 1-60, e.g. NN dioctylcarbamoyl), sulfamoyl group (carbon number 0-6
0° (for example, t-butylsulfamoyl), and R1 and R2 may jointly form a carbocycle or a heterocycle.

R3 represents a substituted or unsubstituted alkylene group (1 to 5 carbon atoms, e.g. methylene, ethylene), and the substituents on the alkylene group include the groups listed above for RR2,
Examples include atoms other than hydrogen atoms.

R', R' Rh, and R are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, fluorine atoms), hydroxyl groups, cyan groups, nitro groups, substituted or unsubstituted alkyl groups (carbon atoms 1 to 60). .For example, cyclohexyl, dodecyl, octadecyl, 3(N,N-dioctylcarbamoyl)propyl), acylamino group (carbon number 2 to 60°, e.g. octanoylamino, 2-hexyldecanoylamino, benzoylamino, nicotinamide), sulfone Amide group (1 to 606 carbon atoms, e.g. hexadecanesulfonamide, dodecyloxybenzenesulfonamide), alkoxy group (1 to 600 carbon atoms, e.g. methoxy, n-butoxy, hexadecyloxy, 2-methoxyethoxy)
, aryloxy group (having 6 to 600 carbon atoms, e.g. phenoxy, 4-t-octylphenoxy), alkylthio group (having 1 to 60 carbon atoms, e.g. methylthio), arylthio group (
6-600 carbon atoms, e.g. phenylthio), amino groups (0-60 carbon atoms, e.g. -NHt, N,N-diethylamino, N,N-dioctadecylamino), acyl groups (2-60 carbon atoms, e.g. acetyl, benzoyl) , lauroyl), acyloxy groups (2 to 600 carbon atoms, e.g. acetyloxy, benzoyloxy, lauroyloxy), carbamoyl groups (1 to 600 carbon atoms, e.g. N, N-dicyclohexylcarbamoyl, N N-dioctylcarbamoyl),
Carbamoyl group (carbon number 1-60, e.g. N'-dodecylcarbamoyl), sulfamoyl group (carbon number 0-60
0 (e.g. N, N-dibutylsulfamoyl), sulfamoylamino group (carbon number 0 to 60, e.g. N', N-dipropylsulfamoylamino), alkoxycarbonyl group (carbon number 2 to 600, e.g. methoxycarbonyl, butoxycarbonyl group), aryloxycarbonyl group (
C7-600 e.g. phenoxycarbonyl), heterocyclic group (5-6 members may have a condensed ring) C1
~600 e.g. octadecyl succinimide, frill,
pyridyl), aryloxycarbonyloxy group (7 to 60 carbon atoms, e.g. phenoxycarbonyloxy), alkoxysniphonyl group (1 to 60 carbon atoms, e.g. methoxysulfonyl, ethoxysulfonyl), aryloxysulfonyl group (6 to 60 carbon atoms, e.g. methoxysulfonyl, ethoxysulfonyl), 600 (for example, phenoxysulfonyl), provided that RS is not a hydroxyl group, and two adjacent groups may jointly form a carbocycle or a heterocycle.

X is -NHCO-1-NIICONH-2-CON)I
-2-NH3O! -n each independently represents O or 1.

The total number of carbon atoms in R1 to R7 is 8 or more.

The compound of formula (I) may form a bis-form, a tris-form or a polymer.

The alkali precursor of the compound represented by the formula ([) of the present invention is the compound represented by the formula (I) in which the hydroxyl group moieties at the 1st and 4th positions of the hydroquinone core have a protective group that can be cleaved under alkaline conditions. Protecting groups include acyl groups (e.g. acetyl, chloroacetyl, dichloroacetyl, benzoyl, 4-cyanobenzoyl, 4-
oxopentanoyl), alkoxycarhomyl groups (e.g. ethoxycarhomonyl, phenoxycarbonyl, 4-methoxybenzyloxycarbonyl), aminocarbonyl groups (e.g. methylaminocaponyl, 4-nitrophenylaminocarbonyl, 2-pyridylaminocarbonyl) , 1-imidaprilcarbonyl), and the protecting groups described in JP-A-59-197037 and JP-A-59-201057. Furthermore, this protecting group may be bonded to each other with R1, R1, R3 or to form a 5- to 7-membered ring if possible, for example)
IN ■ ■ //＼＼ 0＼9 (■ is bonded to the oxygen atom at the 1st or 4th position of the hydroquinone bone nucleus. * represents the bonded part as R1, R2, R3 or X) 2N) RI, Rff
Preferred substituents for i are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or an alkylthio group, and among these, a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group may be used. More preferably, it is a substituted or unsubstituted alkyl group.

In formula (I), preferred R3 is unsubstituted,
or an alkylene group substituted with an alkyl group. Preferred substituents for R', R', R', and R in formula (I) are a hydrogen atom, a substituted or unsubstituted alkyl group, an acylamino group, and a sulfonamide group, respectively. , an alkoxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxysulfonyl group, among which a hydrogen atom, a substituted or unsubstituted alkyl group, an acylamino group, a sulfonamide group, a carbamoyl group, an alkoxy More preferably, it is a carbonyl group.

Preferably, X is -NHCO-.

The sum of m and n is preferably 2 or less, m is very preferably 1, and n is relatively preferably O.

The total number of carbon atoms of R1 to R7 in formula (I) is preferably 8 or more.

Specific examples of compounds included in formula (I) of the present invention are listed below, but the present invention is not limited thereto.

CH3 tHs υn cqH+q(n) CH.

C, lI.

shi113 υ■ υH shirI3 shi11°υN CJt (n) shi4Hw(tJ C,H9 Next, a typical method for synthesizing the compound included in 2(I) of the present invention will be shown.

Synthesis Example 1 Synthesis of Exemplified Compound (I) 1-1) 52.5 g of n-nonyl 2-hydroxy-5-methylphenyl ketone was dissolved in 100 d of ethanol, and 9
．． A solution prepared by dissolving 1 g' of sodium hydroxide in 50 d of water containing 1.1 g of sodium hydroxide was added dropwise. After stirring for 2 hours at 40°C, 100 ad! was added, and 20 d of acetic acid was slowly added dropwise. After 0 drops, the reaction mixture was extracted with ethyl acetate, the organic layer was concentrated, 200 d of hexane was added, and the precipitated crystals were filtered. 47.
1 g of 2-(I-hydroxydecyl)-4-methylphenol was obtained.

1-2) Dissolve 6 g of 2-(I'-hydroxydecyl)-4-methylphenol L obtained above and 10 g of tert-butylhydroquinone in 50 m of ethyl acetate,
of concentrated hydrochloric acid was added. After stirring at room temperature for 5 hours, the reaction mixture was poured into 100% water and extracted with ethyl acetate. The organic layer was concentrated, and the obtained oil was purified by silica gel column chromatography (chloroform/ethyl acetate = 10/I) to obtain the target compound (5) of Ilg as a white powder.

Elemental analysis value Cnea 8.41χ H: 10.01χ Calculated value Cnea 8.60χ Old 9.77χ Synthesis example 2 Synthesis of exemplified compound (6) 2-1) 21g of 2-hydroxy-5-aminoacetophenone was dissolved in acetonitrile 200I11 , dimethylacetamide LooId, and pyridine 13°51d, and 28.7 g of hexadecanoyl chloride was added dropwise at room temperature. After stirring for 1.5 hours, the reaction mixture was diluted with water 2
00d, and the precipitated crystals were filtered and washed with acetonitrile. After drying, 40.5 g of 5-hexadecanoylamino-2-hydroxyacetophenone was obtained.

2-2) 40 g of 5-hexadecanoylamino-2-hydroxyacetophenone obtained above was mixed with 5 ml of ethanol.
00d, and 4.3 g of sodium borohydride was added. After stirring at 40"C for 1.5 hours, the reaction mixture was poured into 500ml of water, made weakly acidic with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration. After drying, 26.7g of 2-(I'-hydroxy Ethyl)-4-hexadecanoylaminophenol was obtained as crystals.

2-3) 24 g of 2-(I'-hydroxyethyl)-4-hexadecanoylaminophenol obtained above
9.7 g of tert-butylhydroquinone were dispersed in 150 Id of ethyl acetate, 4.8 d of concentrated sulfuric acid was added dropwise at room temperature, and the mixture was stirred at 35° C. for 1.5 hours. After adding 200 d of water to the reaction mixture, separating the organic layer and washing with water,
The solvent was distilled off under reduced pressure.

The residue was crystallized with 50 ml of ethyl acetate and 100 ml of n-hexane, and after drying, 15.3 g of the target compound (6) was obtained. (m
p160~161°C) Elemental analysis value C near 5.69χ H: 9.81%
N: 2.702 Calculated value C near 5.65χ) I: 9.
90χ ) l:2.59χ Synthesis Example 3 Synthesis of Exemplified Compound (I3) 25.4 g of tert-octylhydroquinone and 27 g of 2-hydroxymethyl-4,6-di-tert-butylphenol were dissolved in 100 d of acetic acid and concentrated at room temperature. Sulfuric acid 0.
Added 4d. After further stirring at 40°C for 4 hours, the reaction solution was poured into 100% cold water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and crystallized by adding n-hexane to the residue. The obtained crystals were dried to obtain 13.2 g of the desired product (I3). (mpl
B8~190'C) Elemental analysis value C near 9.10χ 11:10.01
χ Calculated value C Near 9.04χ ll: 10.06χ Since the compound of the present invention is intended to be used as an agent to prevent color staining and color fog in photographic materials, the compound itself may be colored or the developing process may Forming a color image with the photosensitive material impedes good color reproduction of the photographic material and defeats the purpose. Therefore, firstly, the compounds of the invention are substantially colorless.

Substantially colorless means 400nm to 70nm.
This means that the compound of the present invention does not have absorption with a molar extinction coefficient of 5,000 or more in the visible wavelength range up to 0 nm.Secondly, the compound of the present invention has a coupling reaction with an oxidized form of a color developing agent within its molecule to form a color image. It does not have coupler residues known to form (e.g. acylacetanilide residues, 5-pyrazolone residues, 1-naphthol residues/groups, etc.) and forms color images through coupling reactions during the development process. Never.

The compounds of the present invention can be used in layers in a sensitive material, such as light-sensitive emulsion layers (blue-sensitive layer, green-sensitive layer and red-sensitive layer) or their adjacent layers (for example, intermediate layers adjacent to different color-sensitive emulsion layers and (e.g., an intermediate layer sandwiched between substantially the same color-sensitive emulsion layers), a protective layer, an antihalation agent, etc., but preferably an intermediate layer sandwiched between emulsion layers with different color sensitivities. Contain in the layer.

The amount of the compound of the present invention added ranges from 1X10-' to 1
10-" mol/n (preferably 10-6 to 3 x 10-3 mol/n, more preferably 1 x 1
0-S to 1 x 10-'' pieces 01/po.In the case of a silver halide emulsion layer, the silver halide contained in that layer is 1/Po.
per mole from 1X10-' to 1 mole, preferably 3X10
-' to 3X10-' moles, more preferably 1x10-'
3 to I x 10-' mol.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number and details of the layers and non-photosensitive layers.A typical example is to use a plurality of silver halides with substantially the same color sensitivity but different photosensitivity on the support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of an emulsion layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 1343.8, No. 59-113440, No. 61-2
Coupler, DIR compound, etc. as described in No. 0037 and No. 61-20038 aA specifications may be included, and a color mixing inhibitor as commonly used may be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1.121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the halogen emulsion layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. 57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitivity H (to I ,)/
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
) or 811/BL/GL/GH/R1(/R
L order, or 8+1/8L/G) I/Gt, /RL/
They can be installed in the order of RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GI=/RI. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-malignancy emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is about 2 mol % to about 25 mol %.
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23, "'1. Emulsion preparation and
d types)”, and Nα18716 (I9
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, GIafki
des, Chemic et Ph1sique P
photograph-ique, Paul Mont
el+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
mistry (Focal Press+1966)
), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focalb L/S.
tal,, gate making and coating
Photographic Emul-sion+F
ocal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (I970); U.S. Patent No. 4
, 434,226, 4.414.310, 4.
433.048, 4,439,520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to research disclosure restrictions17.
643 and the same No. 18716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral enhancers,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right, 4 Brighteners Page 24 5 Antifogging agents Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorbers, pages 25-26 Page 649 right column ~ Filter dyes, Page 650 left column Ultraviolet rays Absorbent 7 Anti-stain agent Page 25 right i Page 650 left-right column 8 Dye image stabilizer Page 25 9 Hardener page 26 65° Page 1 left column lO
Binder page 26 Same as above 11 Plasticizer,
Lubricant Page 27 Page 650 Right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static Page 27 Same as above Patch In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) k 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4.314,
No. 023, No. 4.511,649, European Patent No. 24
No. 9,473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, European Patent No. 4.351,897, European Patent No. 73.636, U.S. Patent No. 3,061,432, U.S. Patent No. 3.725,067, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure Sou 242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
5-118034, 60-185951, U.S. Patent No. 4500.630, 4,540,654, 4,556,630, International Publication No. 088104
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052,212.
No. 4,146,396, No. 4.228.23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895,826, No. 3.772
, No. 002, No. 3,758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
No. A, No. 249453A, U.S. Patent No. 3.446,
No. 622, No. 4,333.999, No. 4,775
, No. 616, No. 4,451.559, No. 4,42
No. 7,767, No. 4,690,889, No. 4,
254.

No. 212, No. 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure Nα17643, Section ■-G, U.S. Patent No. 4,163,670, and Japanese Patent Publication No. 5
No. 7-39413, U.S. Pat. No. 4,004,929
No. 4,138,258, British Patent No. 1,146
, 368 are preferable, and couplers that correct unnecessary absorption of coloring dyes by fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774,181 and U.S. Pat. No. 4,777 It is also preferable to use a coupler having as a leaving group a dye precursor group which reacts with a developing agent to form a dye as described in No. 120.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DLR coupler emitting the development inhibiting side is the aforementioned RD 17643.
, Patent described in Sections ■ to F, Japanese Patent Application Laid-open No. 1519-1983
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, U.S. Patent No. 4,248,9
No. 62 and No. 4°782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing couplers,
DIR coupler releasing redox compound or DIR redonx releasing redox compound, European Patent No. 17330
Couplers that release dyes that give aftercolor after separation as described in No. 2A, R, D, Nα11449, Nα24241, JP-A No. 6
Bleach accelerator-releasing couplers described in US Pat. No. 1-201247, Gantt-releasing couplers described in US Pat. Cylinder 4.774,1
Examples include couplers that emit fluorescent dyes as described in No. 81.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
A specific example of the above-mentioned high boiling point organic solvent is phthalate! [(dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis-iz, 4-di-t-amylphenyl) phthalate, bis(2,4-di-z).

amyl phenyl) isotucrate, bis(I,1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethyl hexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexylbenzoate, etc.)
-ethylhexyl-p-hydroxybenzoate, etc.)
, amides (N,N-diethyldodecanamide, N,N
-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-di-tert-amylphenol, etc.)
-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-ptoxy-5-tert-octylaniline, etc.), hydrocarbons (Paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is approximately 30°C.
As mentioned above, organic solvents with a temperature of preferably 50°C or more and about 160'C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. It will be done.

Specific examples of the latex dispersion process, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and Patent Application No. 1983-
Benziisothiazolone, n-butyl p-hydroxybenzoate, phenol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is described from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate Trot is preferably 30 seconds or less.

Film thickness is 55% relative humidity at 25°C! J Means the film thickness measured under humidity (2 days), and the film swelling rate TI/! can be measured according to techniques known in the art.

For example, Photography Science and Engineering (Photogr, Sci, Eng,) + 19 by Green, et al.
It can be measured by using a swellometer of the type described in @, No. 2, pages 124-129, and T,
/2 is the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds, and this T
It is defined as the time required to reach 1/2 film thickness.

Membrane swelling rate T17. can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula = (maximum swollen film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention can be developed by the conventional method described in the above-mentioned RD, pages 28 to 29 of 17643, and the left column to right column of 615 of Nα1B716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenyl diamine compounds are preferably used, and a typical example is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pn buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazide, triethanolamine, catechol sulfonic acids, triethylenediamine (I,4-diazabicyclo(2,2,2)octane), etc. various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifying layers, aminopolycarboxylic acids, aminopolymer Various calcinants such as phosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxy Ethylidene
1,1-diphosphonic acid, nitrilo-4,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N-
Tetramethylenephosphonic acid, ethylene glycol (0-
Typical examples include hydroxyphenylacetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, high p)l, and a high concentration of color developing agent. .

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. As a bleaching agent, for example, iron (RFI), Kobal)
Compounds of polyvalent metals such as (ill), chromium (IV), and ail (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide-dichromate; organic complex salts of iron (I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates including ethylenediaminetetraacetic acid iron (mHf salt) are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (I[[) Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions.The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(I[I) complex salts is usually 5.5 to 8. However, it is also possible to process at an even lower pi (to speed up the process).

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or disulfide group as described in No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706.561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16.235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compound described in No. 8836; Others
-42,434, 49-59.644, 53-
9.4.927, 54-35.727, 55-
Compounds described in No. 26.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West Patent No. 1゜290.812, JP-A-53-9
Preferred are the compounds described in US Pat. No. 5,630, and also preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material.
These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for shadows.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers Volume 64, P, 24
8-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J, Hygiene technology side note" It is also possible to use the disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidone may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
1; No. 44547, and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C.9 Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A No. 60433449, No. 59
It can also be applied to thermal development window optical materials described in European Patent No. 218443, European Patent No. 61-238056, and European Patent No. 210.66OA2.

(Left below) When the compound of the present invention is used in a color diffusion transfer photographic light-sensitive material, the dye image-providing compound used in combination with the silver halide emulsion layer is negative-type and treated with an alkaline processing composition. initially mobile or non-mobile within the photographic element.

Negative-working dye image-providing compounds useful in this invention include couplers that react with oxidized color developing agents to form or release dyes, specific examples of which are U.S. Pat.
No. 550 and Canadian Patent No. 602,607. Preferred negative dye image-providing compounds for use in the present invention C include dye-releasing redox compounds in which a developing agent or an electron transfer agent in an oxidized state reacts to release a dye; typical examples thereof include is US patent 3゜9
28.312, 4,135,909, 405
5 428, 4,336,322, 4,053
, No. 312, etc.

The dyes formed from the dye image-providing compounds used in this invention may be ready-made dyes or alternatively may be dye precursors that are converted into dyes in photographic processing steps or additional processing steps, resulting in the final image dye. may or may not be metal complexed.

Representative dye structures useful in the present invention include metal-complexed and non-metal-complexed dyes such as Ab dyes, azomethine dyes, anthraquinone dyes, and phthalocyanine dyes.

Among these, cyan, magenta and yellow dyes are particularly important.

Also, as a type of dye precursor, a dye-releasing redox compound having a dye moiety that temporarily shifts light absorption in a photosensitive element can also be used in this patent; a specific example thereof is disclosed in U.S. Pat. , same T-999,0
No. 03, No. 3.336287, No. 3,579.334
No. 3982.946, British Patent No. 1,467.31
No. 7 and Japanese Unexamined Patent Publication No. 57-158638.

Processes for obtaining color diffusion transfer images using dye-releasing redox compounds are described in Photographic Ink Science and Engineering J.
photographic 5science andEn
gineering) magazine, vo120, Nn:4
, p. 155-164, July/August
1976.

Any silver halide developer can be used in the above process as long as it is capable of cross-oxidizing the dye-releasing redox compound. Such developing agents may be included in the alkaline processing composition or in appropriate layers of the photographic element. Examples of developing agents that can be used in the present invention are as follows: hydroquinones, aminophenols, phenylenediamines, and pyrazolidinones (e.g., phenidone, 1-phenyl-3- Pyrazolidinone, dimedun (i.e. 1-phenyl 4,4-dimethyl-3
-pyrazolidinone), IP-) true 4-methyl-4-
oxymethyl 3-pyrazolidinone, 1-(4'-methoxyphenyl)-4-methyl-4-oxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidinone] and the like.

Processing compositions used to process photographic elements according to color diffusion transfer processes can include a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, and have a pH of about 9 or higher. suitable, preferably having an alkaline strength of 11.5 or higher. The treatment composition may contain antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may also contain silver ion concentration regulators such as potassium bromide. It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for the sensitizing dye, the coating amount of -lff1 per mole of silver halide is shown in mole units.

(Sample 101) 1st layer (antihalation layer) Black colloidal silver Silver 0.1 day gelatin 1.40 2nd N (intermediate layer) 25-G-L-pentadecylhydroquinone 0.18EX-
10,07 E -2 EX-1゜B5-1 Gelatin 4th layer (second red-sensitive emulsion N) Emulsion C Enhancement dye I 0.002 0.0G 0.08 0.10 0.10 0.02 1.04 Primate 0. 25 Silver 0.25 6.9X10-5 1.8xlO-5 3,1X10-' 0.335 0.020 0.060 0.87 i1.0 5.1X10"' Sensitizing dye ■ Sensitizing dye m EX -2 EX-3 EX-10 B5-1 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion enhancing dye■ Sensitizing dye■ Enhanced dye■ EX-3 X-4 EX-2 B5-1 HB S- 2 Gelatin 6th layer (intermediate layer) Comparative compound A-1 1,4X10-'2.3XlO-' 0.400 0.050 0.015 0.060 1.30 Silver 1.60 5.4X10-' 1. 4X10-5 2.4X10-' 0.010 0.080 0.097 0.22 0.10 1.63 0.018 HB S-1 Gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Increase Sensitizing dye V Enhanced dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 EX-8 HB S -1 B5-3 8th gelatin layer (second glaucoma emulsion layer) Emulsion C Enhanced dye V Sensitizing dye ■ Sensitizing dye ■ 0.020 0.80 Silver 0.15 1 bar 0.15 3.0X10-'1.0X10-'3.8X10-' 0.260 0.021 0.030 0.025 o, to.

O,010 0,63 ! 1 0.45 2, lX10-' 7.0X10-' 2.6 x 10-' ImiX-6 EX-8 EX-7 11B S-1 +1 B S-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Sensitizing dye■ Sensitizing dye■ Exacerbating pigment■ EX-13 EX-11 EX-1 B5-1 B5-2 gelatin 10th layer (yellow filter layer) yellow colloidal silver Comparative compound A-1 0,094 0,01)+ 0.026 0,1fli.

O,008 0,50 i 艮　　　1.2 3.5X10”5 s, ox to-' 3.0X10”’ 0.015 0.100 0.025 0.25 0.10 1.54 i 艮 0.05 0.036 )IBS-1 gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye■ X-9 X-8 HB S-1 gelatin 12th layer (second blue emulsion layer) Emulsion G Sensitizing dye■ X-9 X-10 B5-1 gelatin 13th layer (3rd blue emulsion jii) Emulsion H 0,03 0,95 Silver 0.08 Resentment 0.07 1!0.07 3.5X10-' 0.721 0.042 0.28 1.10 Silver 0.45 2, lX10-' 0.154 0.00? 0.05 0.78 Sensitizing dye■ X-9 B5-1 gelatin 14th N (1st protection N) Emulsion ■ B5-1 gelatin 15th layer (2nd protection N) polymethyl acrylate particles (Diameter approximately 1.5μm) gelatin In addition to the above ingredients, each layer contains H-1 and a surfactant were added.

Silver 0.77 Silver 2.2X10-' 0.20 0.07 0.69 0.5 0.11 0.17 0.05 1.00 0.54 0.20 1.20 Gelatin Hardener X-1 l X-2 01X-3 0■ X-4 0H X X X-12 l C,ll, O3Oρ X-7 X-8 X-9 B5-2 Di-n-butyl phthalate sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ CTo=(JI SOx CHt C0NHL:
hA-1 (compound of U.S. Pat. No. 2,336.327 (
6)) A-4 (Compound (2) of Japanese Patent Publication No. 55-7578
)0 ■ H A-2 (Compound (I) of U.S. Pat. No. 4,277.553
)) A-5 (Compound (9) of U.S. Pat. No. 2,701,197) H H A-3 (Compound 1-22 of U.S. Pat. No. 4,277, 558) H H Sample (I02-111) Sample Instead of comparative compound A-1 in the sixth layer of No. 101,
Comparative compounds A-2, A-3, A-4 and A-5 were replaced with compounds (I), (6), (I3), (21) of the present invention.
Samples 102 to 110 were prepared in the same manner as Sample 101 except that equimolar amounts of ), (27), and (33) were replaced.

These samples were exposed to red light for scratches and subjected to the following color development process. Measure the density of the sample after processing with a red filter and a green filter, and calculate the value obtained by subtracting the magenta Capri density from the magenta density at an exposure amount that gives a cyan fill measured with the red filter of 4 degrees (Capri + 1° 5). The color turbidity is summarized in Table 1.

The development used here was carried out at 38°C as described below.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, fixed, 1 minute 05 seconds The treatment liquid composition used in each step is as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β- Hydroxyethylamino)-2 Add 2-methylnaniline sulfate and add 4.5g 1,01 pH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Add water 10°150°10°I.

pH6゜ Fixer Ethylenediaminetetraacetic acid disodium lium salt sodium sulfite Ammonium thiosulfate aqueous solution (70%) sodium bisulfite add water 1.0g 4.0g ■　75゜ 4゜ l.

pH6゜ Stabilizer Formalin (40%) polyoxyethylene-p-mono nonylphenyl ether (Average degree of polymerization ÷ 10) add water 2, 0d 0.3g 1.0ffi Table 1 The value obtained by subtracting the capri magenta density from the density.

In addition, these samples were left for (A) 7 days at 25°C and 60% relative humidity, and (B) 7 days at 40'C and 80% relative humidity, and then imagewise exposed to white light. The color development described above was performed. The concentration of these processed samples was measured (
Table 1 summarizes the respective densities under condition (B), which is a forced deterioration condition at an exposure amount such that yellow-magenta and cyan densities are each 1.5 under condition A).

From Table 1, the degree of color turbidity is samples 106 to 111 of the present invention.
Samples 104 and 105 are small (and it can be seen that the compounds used in these samples have a high ability to prevent color staining. However, sample 104 has a large degree of color muddiness observed at yellow density, and its ability to prevent color staining is low. Yes, it is not practical.

Also, from Table 1, after being placed under forced deterioration conditions, sample 1
It was found that the magenta density and cyan density of Sample No. 05 significantly decreased, whereas the photographic performance of the sample of the present invention showed only a slight decrease, demonstrating the effectiveness of the present invention.

Example 2 A multilayer color photographic paper 201 having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-6)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was diluted to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. On the other hand, the blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, containing 0.2 mol% silver bromide on the grain surface). Sulfur sensitization was prepared after addition of 2.0 x 10-' moles per mole of each. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. The coating liquid for the second to seventh layers is also
It was prepared in the same manner as the layer coating solution. The gelatin hardening agent for each layer is l-oxy-3,5-dichloro-5-1-
Riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (each 4.OX10-' mol per 1 mol of silver halide)
and 5O8 SO, I+.(CtHs)x (each 7.OXl0-' mol per mol of silver halide)
SOl SOffH・(CJs) s (each 2.OXl0-' mol per mol of silver halide)
Red-sensitive emulsion layer xto-' moles, 2.5 x 10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

tH5 1-CsH+ + (0.9X10-4 moles each per mole of silver halide) To the red-sensitive emulsion layer, the following compounds were added at 2.6X10-' moles per mole of silver halide.

and also 1-(5-methylureidophenyl)-5-mercaptotetrazole for each mole of silver halide for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer.
．． 5X10-'mol, 7,7 (layer structure) The composition of each layer is shown below, and the numbers represent the coating amount (g/po). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye (ulmarine)] -th layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) '0.19m capacity (Solv-1
) 0. 35 Color image stabilizer (Cpd-6) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-4) 0.08 Solvent (Solv
-2) 0.16? Container (Solv-
3) 0. 08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (1:3 mixture (Ag mole ratio) of one with a cubic average grain size of 0.55μ and one with a cubic average grain size of 0.39μ), coefficient of variation of grain size distribution 0 each , 10.0.08, and each emulsion contained 8 mol % of AgBr O locally on the grain surface.

Gelatin magenta coupler (ExM) Color image stabilizer (Cpd-3) Color image stabilizer (epa-'y) Color image stabilizer (Cpd-6) Solvent (Solv-4) Solvent (Solv-3) Solvent (Solv- 7) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-4) Solvent (Solv-5) Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic average grain 1=4 mixture of size 0.58μ and 0.45μ (
Agtl ratio), particle size distribution 0, 12 1, 24 0, 27 0, 15 0.005 0.007 0, 18 0.18 coefficient of variation each 0.09. ．． 0.11, AgBr for each emulsion
6 mol % of O was locally contained on a part of the particle surface.
0.23 gelatin
1.34 cyan coupler (ExC+)
0.32 color image stabilizer (Cpd-5) 0
．． 17 Color image stabilizer (Cp d-2) 0.
04 capacity (Solv-6)
0. 45 polymer (P-1)
0.40 latex <C-X> 0.20 as a polymer component 6th layer (ultraviolet absorbing layer) Gelatin 0.53 ultraviolet absorber (uv-1) 0.16 color mixing inhibitor (C
pd-4) o, 02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (ExY) Yellow coupler (E x M) Magenta coupler (ExC+ ) Cyan coupler (Cpd-3) Color image stabilizer (Cpd-4) Mixing inhibitor H H (Cpd-5) Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer 1:1 mixture (Cpd-6) color image stabilizer! (Cpd-7) Color image stabilizer (UV-1) Ultraviolet vA absorber (Solv-2) Medium H (Solv-3) ? Solv-4? 8 medium (S01ν l) ton capacity 0-P-(-0-(-C11t)6-CllCllx)
(P4) Color image stabilizer 1←C1l□-C1l→bottom- C0NHCaH7(t) (Number average molecule i60.000) (Solv-5) Solvent C2H4 COOCHzCHCJq (n) Js (Solv-6) 250 CMS in l8 medium I went to become an exposed mouse.

The above-exposed sample is continuously processed using an automatic paper processing machine until twice the tank capacity of the color developer is replenished in the second half processing step and processing composition (running test).
was carried out.

In the second layer of this sample 201, sample 201 was used except that the compounding movement and amount of formula (I) were changed as shown in Table 2.
Samples 202 to 212 similar to Example 1 were prepared.

The following experiment was conducted to examine the photographic properties of these samples.

First, using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure time at this time was 1/10 second color development 38'C4
5 seconds '109d 41 bleach-fix 30-36"C4
5 seconds 205 Rinse 41 Rinse ■ 30-37°C
20 seconds -21 rinse ■ 30-37'C 20 seconds -21 rinse ■ 30-37'C 20 seconds 36
4d 21 Drying 70 to 85° C. 60 seconds *Amount of replenishment per 1M of photosensitive material (3 tank countercurrent system from rinse ① to ② was used.) The composition of each processing solution is as follows.

h--Dantaka iLz Bungyo 3fLlfJL Wed 800d
800d ethylenediamine-N.

N,N',N'-tetramethylenephosphonic acid 5,6-cyhydroxybain-2,4-disulfonic acid triethanolamine sodium chloride potassium bromide potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)- 3-methyl=4-aminoaniline sulfate N,N-bis(carboxymethyl)hydrazine Sodium sulfite optical brightener (Sumitomo Chemical rWHITEX-4J diaminostilbene type) Add water 5.0g 0.5g 8.0g 2 .4g 0.015 g 5g 5.0g 0.03mo1 0.02g 1, Og 000d 5.0g pH (25°C) 10.05 0.5g 8.0g O,Og O,Og 5g Dish mourning (tank liquid and replenisher are the same) Ammonium hydrothiosulfate (70%) Ammonium sulfite 10.50 00d 00d 1g 9.5g 0.05mol 0.02g 2.5g 1000, wffl Iron(III) ethylenediaminetetraacetate Ammonium 55g Disodium ethylenediaminetetraacetate 5g glacial acetic acid
' Add 9g ammonium bromide 30g water
I 000 ml pH (25°C) 5.
40 The rinsing solution used was ion-exchanged water with calcium ion/magnesium ion content of a pH11 or less.

Using the sample after the above processing, the maximum density of each color of yellow, magenta, and cyan and the degree of magenta color mixing at a yellow density of 2.20 ([magenta density at a yellow density of 2.20] - [yellow Magenta density) was evaluated.

The results are shown in Table 2.

Regarding color mixture in the table, the smaller the number, the less the amount. Therefore, the compound of the present invention has an excellent ability to prevent color mixing (color fog),
It is clear that sufficient effects can be obtained with a small amount added.

Note that the fourth layer of samples (202) to (212)
Add the same amount of octylhydroquinone to each second
Similar results were obtained by replacing the layer with the compound of the present invention.

Example 3 Photosensitive sheet A was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate film support.

(I) Copoly[styrene-N-vinylhensyl-N
N,N-1 lyhexylammonium chloride]-3,0
g/nf, gelati 73. Mordant layer containing Og/rrr.

(2) A light reflecting layer containing 20 g/po of titanium dioxide and 2.08 g/po of gelatin.

(3) A light shielding layer containing 3.0 g/rrf of carbon black and 2.0 g/rd of gelatin.

(4) Magenta dye-releasing redox compound 0 with the following structure
．． A layer containing 65 g/nf and 1.2 g/nf gelatin.

(5) Green-sensitive internal latent image type direct reversal silver bromide emulsion (silver amount 1.2g/n), gelatin (I,3g/r+(), image nucleating agent with the following structure (0.04mg/n) () and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0,12 g/rd).

(6) A layer containing the compound Q hot water of the present invention, 0.45 g/po and tricyclohexyl phosphate 0.2 g/rrf.

(7) A layer containing yellow dye-releasing redox compound '370.75 g/rrf of the following ff1I structure, 0.2 g/rrf of tricyclohexyl phosphate, and 1.2 g/+d of gelatin.

(8), layer containing gelatin (I, 0g/n?). Photosensitive sheet B and photosensitive sheets C and D as comparative samples were prepared in the same manner.

- Photosensitive sheet B: the same molar amount of 2,5-di-L-pentadecylhydroquinone described in JP-A-54-29637 instead of the compound of the present invention as a color stain preventive agent in layer (6) of photosensitive sheet A; Same photosensitive sheet as A except that 0.49g/rrf was replaced.

- Photosensitive sheet C: The color stain preventive agent for layer (6) of photosensitive sheet C is compound (22) of U.S. Pat. No. 4,277.55 No. 3, 2-sec-octadecyl-5.
- The same photosensitive sheet as A except that the same molar amount of benzenesulfonylhydroquinone was replaced with 0.47 g/bo.

・Photosensitive sheet D = Layer (7) and N (8) of photosensitive sheet A
Same photosensitive sheet as A except that it is not coated with.

A cover sheet was prepared with the following layers applied in sequence on a transparent polyester support.

(I) Polyacrylic acid 17 g/rT? , N-hydroxysuccinimidebenzenesulfonate 0.06g
/rr (and ethylene glycol 0.5 g/r+), coated to a thickness of 7 microns.

(2) Timing layer coated with cellulose acetate (oxidation degree 54) to a thickness of 2 microns.

(3) Timing layer coated with a copolymer latex of vinylidene chloride and acrylic acid to a thickness of 4 microns.

A treatment solution having the following composition was prepared.

rl-phenyl-4-hydroxymethyl concentration) obtained the value of

are shown in Table 3.

The value of Db when Dg = 2°0 After the above-mentioned angry light sheet) A-D was exposed with a wedge, it was integrated with the container containing the processing liquid and the cover sheet, and 25
The processing liquid was spread to a thickness of 80 microns using a pressing member under conditions of 35°C and 35°C to obtain a transferred color image. The transferred image was measured with a color densitometer and Dg (green filter density L Db
(Blue filter In the photosensitive sheets A to C prepared here, the layer (6) containing a color stain preventive agent is a silver halide emulsion in which the oxidized developer generated in the layer (5) containing a green-sensitive silver halide emulsion is When diffused through layer (6) in the direction of layer (7) containing a yellow dye-releasing redox compound that is not combined with N(5), it reacts with this oxidized developer and prevents the release of yellow dye. (This prevents the color of magenta from becoming muddy, that is, from mixing yellow with magenta and deteriorating the magenta hue).

Therefore, the ability of the layer (6) containing a color stain preventive agent in photosensitive sheets A, B, and C is the value of Db - Db (photosensitive sheet D).
That is, photosensitive sheet A using the compound of the present invention, which can be judged by the degree of color cloudiness, has a significantly smaller value of color cloudiness than comparative photosensitive sheets B and C, and it is clear that the color stain prevention ability is high. be.

Procedural amendment

Claims (1)

[Scope of Claims] A silver halide color photographic material containing at least one substantially colorless compound represented by the following formula (I) or its alkali precursor. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, acylamino groups, alkoxy groups,
It represents an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, a carbamoyl group, or a sulfamoyl group, and R^1 and R^2 may jointly form a carbocycle or a heterocycle. R^3 represents an alkylene group. R^4, R^5, R^6, R^7 are hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, alkyl group, acylamino group, sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group represents an amino group, an acyl group, an acyloxy group, a carbamoyl group, a carbamoylamino group, a sulfamoyl group, a sulfamoylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkoxysulfonyl group, or an aryloxysulfonyl group. . However, R^
5 is not a hydroxyl group, and two adjacent groups may jointly form a carbocycle or a heterocycle. X is -NH
CO-, -NHCONH-, -CONH-, -NHSO
_2-, -NHSO_2NH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and m and n each independently represent 0 or 1. The total number of carbon atoms in R^1 to R^7 is 8 or more.